• No se han encontrado resultados

The findings of this thesis present a clear indication of the importance of bioavailability when modelling metal toxicity in soil. While the bioavailability models were developed on the basis of toxicity experiments performed in different soils covering a wide range of soil properties, the future use of these models may be limited to the range in soil properties for which they were derived. Nevertheless, we have reasons to be optimistic about regulatory

application of the developed bioavailability models since they provide a mechanistic framework and can be easily modified to incorporate the effects of other toxicity-modifying factors. A series of validation studies and meta-analysis using our model concepts are encouraged to be done in future. Besides, it would be possible to apply our models to geographically oriented databases in order to do GIS-mapping of the site-specific risks of metals on a large scale, as long as the basic soil information (i.e., porewater chemistry) required by the models is available.

Various single-species screening tests are often employed to detect possible harmful effects of metals in soil. In this thesis, earthworms were selected as the test species as they are the dominant soil macrofauna and play a vital role in soil functioning. However, numerous species and a complex food web are exposed in the soil environment. Therefore, a battery of toxicity tests should be used to evaluate the effects on different trophic levels, as well as acute, chronic, and next-generation effects. Until now, very few research efforts have been made to determine the minimum battery of tests needed. To obtain a balanced battery of tests, it is recommended that a series of important criteria for selecting representative species among others need to be met, such as having different life-histories and exposure routes, and belonging to different functional and taxonomic groups. Besides, the selection of a battery of tests should be tailored to specific protection objectives.

Most of the bioavailability models are developed at a fixed time point, while the toxicodynamic part of the model is simply to relate the bioavailable faction (e.g., f value in BLM) to a toxicological endpoint (e.g., LC50 or EC50). This is also the case in our study. However, it has been recognized that bioavailability is not a static but a dynamic phenomenon (see Figure 1.1). For a better understanding of metal bioavailability, the underlying toxicokinetic and toxicodynamic processes deserve further investigation. This kind of research will enable the extrapolation of metal effects in the course of time and from soil organisms to higher organisms.

Our study distinguished the interactions of Cd and Zn at the exposure level from those at the organism level. However, the interactions of metal mixtures observed in this study yield little information about the internal processes involved. In fact, mechanistic pathways of metals inside the organism are poorly known. We therefore recommend that future studies should investigate the mechanisms of mixture interaction and identify the principles of combined toxicity for developing predictive models. Potential topics include, for example, considering the distribution and detoxification mechanisms (i.e., toxicological bioavailability) of one metal in the presence of other metals, and linking mixture effects to the expressions of specific proteins or genes (proteomics and genomics tools).

The issues of metal bioavailability and mixture toxicity have increasingly gained attention on the agenda of risk assessors and risk managers. The findings in this thesis therefore well fit into the broader picture of soil metal risk assessment. Despite the lack of mechanistic understanding of internal processes, the awareness of bioavailability and mixture toxicity has triggered the development of a series of chemical and modelling approaches to normalize the toxicity data in different environmental conditions, and thus has greatly improved risk assessment and standard setting. In case of remediation, environmental regulators are able to choose the sites for remediation where the actual risks are greater rather than blindly choosing the polluted localities where the total metal concentrations are

Chapter VI

126

relatively high. This also avoids unnecessarily strict requirements for cleanup and thus avoids expenditure of funds that could be better used to remediate additional areas. We recommend continuing to discuss and question the relevance of the current approaches for risk assessment and decision making, and to update them according to the available tools and scientific knowledge on bioavailability and mixture toxicity.

Bibliography

Akaike H. 1981. Likelihood of a model and information criteria. J Econometrics 16: 3-14. Ahlf W, Drost W, Heise S. 2009. Incorporation of metal bioavailability into regulatory

frameworks - metal exposure in water and sediment. J Soil Sediment 9: 411-419. Allen HE, Hansen DJ. 1996. The importance of trace metal speciation to water quality

criteria. Water Environ Res 68: 42-54.

Alloway BJ. 1995. Soil processes and the behavior of heavy metals. In: Alloway BJ. (ed.)

Heavy Metals In Soils. Blackie Academic and Professional Publisher, New York.

Almas AR, Lofts S, Mulder J, Tipping E. 2007. Solubility of major cations and Cu, Zn and Cd in soil extracts of some contaminated agricultural soils near a zinc smelter in Norway: modelling with a multisurface extension of WHAM. Eur J Soil Sci 58: 1074-1086. Alsop DH, Wood CM. 2000. Kinetic analysis of zinc accumulation in the gills of juvenile

rainbow trout: effects of zinc accumulation and implications for biotic ligand modelling.

Environ Toxicol Chem 19: 1911-1981.

Altenburger R, Walter H, Grote M. 2004. What contributes to the combined effect of a complex mixture? Environ Sci Technol 38: 6353-6362.

Antunes PMC, Kreager NJ. 2009. Development of the terrestrial biotic ligand model for predicting nickel toxicity to barley (Hordeum Vulgare): Ion effects at low pH. Environ

Toxicol Chem 28: 1704-1710.

Antunes PMC, Berkelaar EJ, Boyle D, Hale BA, Hendershot W, Voigt A. 2006. The biotic ligand model for plants and metals: Technical challenges for field application. Environ

Toxicol Chem 25: 875-882.

Ardestani MM, Ortiz MD, Van Gestel CAM. 2013. Influence of Ca and pH on the uptake and effects of Cd in Folsomia candida exposed to simplified soil solutions. Environ Toxicol

Chem 32: 1759-1767.

Ardestani MM, Van Gestel CAM. 2013. Using a toxicokinetics approach to explain the effect of soil pH on cadmium bioavailability to Folsomia candida. Environ Pollut 180: 122- 130.

Baas J, Van Houte BPP, Van Gestel CAM, Kooijman SALM. 2007. Modelling the effects of binary mixtures on survival in time. Environ Toxicol Chem 26: 1320-1327.

Backhaus T, Faust M. 2012. Predictive environmental risk assessment of chemical mixtures: a conceptual framework. Environ Sci Technol 46: 2564-2573.

Baird DJ, Rubach MN, Van den Brinkt PJ. 2008. Trait-based ecological risk assessment (TERA): The new frontier? Integr Environ Assess Manag 4: 2-3.

Barata C, Baird DJ, Nogueira AJA, Soares AMVM, Riva MC. 2006. Toxicity of binary mixtures of metals and pyrethroid insecticides to Daphnia magna Straus. Implications for multi-substance risks assessment. Aquat Toxicol 78: 1-14.

Barnett AJ, Finlay K, Beisner BE. 2007. Functional diversity of crustacean zooplankton communities: towards a trait-based classification. Freshw Biol 52: 796-813.

Baskin Y. 2005 Under ground: how creatures of mud and dirt shape our world. Shearwater

Books, Island Press, Washington D.C. UAS.

Batley GE, Apte SC, Stauber JL. 2004. Speciation and bioavailability of trace metals in water: progress since 1982. Aust J Chem 57: 903-919.

Bibliography

128

Bengtsson G, Tranvik L. 1989. Critical metal concentrations for forest soil invertebrates.

Water Air Soil Pollut 47: 381-417.

Bliss CI. 1939. The toxicity of poisons applied jointly. Ann Appl Biol 26: 585-615.

Blouin M, Hodson ME, Delgado EA, Baker G, Brussaard L, Butt KR, Dai J, Dendooven L, Peres G, Tondoh JE, Cluzeau D, Brun JJ. 2013. A review of earthworm impact on soil function and ecosystem services. Eur J Soil Sci 64: 161-182.

Bongers M. 2007. Mixture toxicity of metals to Folsomia candida related to (bio)availability in soil. PhD thesis. Free University, Amsterdam.

Borgmann U, Norwood WP, Dixon DG. 2004. Re-evaluation of metal bioaccumulation and chronic toxicity in Hyalella azteca using saturation curves and the biotic ligand model.

Environ Pollut 131: 469-484.

Bouché MB. 1977. Strategies lombriciennes. In: Lohm U, Persson T. (eds) Soil organisms as components of ecosystems. Ecol Bull 25: 122-132.

Brock TC. 2013. Priorities to improve the ecological risk assessment and management for pesticides in surface water. Integr Environ Assess Manag 9: e64-74.

Brown PL, Markich SJ. 2000. Evaluation of the free ion activity model of metal-organism interaction: extension of the conceptual model. Aquat Toxicol 51: 177-194.

Brzóska MM, Moniuszko-Jakoniuk J. 2001. Interactions between cadmium and zinc in the organism. Food Chem Toxicol 39: 967-980.

Butt KR. 1993. Reproduction and growth of three deep-burrowing earthworms (Lumbricidae) in laboratory culture in order to assess production for soil restoration. Biol Fertil Soils 16: 135-138.

Calamari D, Alabaster JS. 1980. An approach to theoretical models in evaluating the effects of mixtures of toxicants in the aquatic environment. Chemosphere 9: 533-538.

Campbell PGC. 1995. Interactions between trace metals and aquatic organisms: A critique of the free-ion activity model. In Tessier A, Turner DR. (eds) Metal Speciation and

Bioavailability in Aquatic Systems. John Wiley, New York, USA, pp 46-102.

Caren N, Panofsky A. 2005. TQCA: a technique for adding temporality to qualitative comparative analysis. Socio Meth Res 34: 147-172.

Cataldo DA, Garland TR, Wildung RE. 1983. Cadmium uptake kinetics in intact soybean plants. Plant Physiol 73:844-848.

Chapman PM, Allen HE, Godtfredsen K, Z’Graggen MN. 1996. Evaluation of bioaccumulation factors in regulating metals. Environ Sci Technol 30: 448-452.

Conder JM, Lanno RP. 2000. Evaluation of surrogate measures of cadmium, lead, and zinc bioavailability to Eisenia fetida. Chemosphere 41: 1659-1668.

Criel P, Lock K, Van Eeckhout H, Oorts K, Smolders E, Janssen CR. 2008. Influence of soil properties on copper toxicity for two soil invertebrates. Environ Toxicol Chem 27: 748- 1755.

Curry JP, Schmidt O. 2007. The feeding ecology of earthworms – A review. Pedobiologia 50: 463-477.

Dallinger R. 1993. Strategies of metal detoxification in terrestrial invertebrates. In: Dallinger R, Rainbow PS, eds., Ecotoxicology of Metals in Invertebrates. Lewis, Boca Raton, FA, pp 245-289.

soils: a review. J Environ Qual 34: 1707-1745.

Das P, Samantaray S, Rout GR. 1997. Studies on cadmium toxicity in plants: a review.

Environ Pollut 98:29-36.

Davis ROE, Bennett HH. 1927. Grouping of soils on the basis of mechanical analysis. United States Department of Agriculture Departmental Circulation No. 419.

De Boer TE, Taş N, Braster M, Temminghoff EJM, Röling WFM, Roelofs D. 2011. The influence of long-term copper contaminated agricultural soil at different pH levels on microbial communities and springtail transcriptional regulation. Environ Sci Technol 46: 60-68.

De Lange HJ, Kramer K, Faber JH. 2013. Two approaches using traits to assess ecological resilience: A case study on earthworm communities. Basic Appl Ecol 14: 64-73.

De Schamphelaere KAC, Janssen CR. 2002. A biotic ligand model predicting acute copper toxicity for Daphnia magna:  The effects of calcium, magnesium, sodium, potassium, and pH. Environ Sci Technol 36: 48-54.

De Schamphelaere KAC, Janssen CR. 2004 Development and field validation of a biotic ligand model predicting chronic copper toxicity to Daphnia magna Environ Toxicol

Chem 23: 1365-1375.

De Vries W, Curlik J, Muranyi A, Alloway B, Groenenberg BJ. 2005. Assessment of relationships between total and reactive concentrations of cadmium, copper, lead and zinc in Hungarian and Slovakian soils. Ekologia-Bratislava 24: 152-169.

De Vries W, Lofts S, Tipping E, Meili M, Groenenberg J, Schütze G. 2007. Impact of soil properties on critical concentrations of cadmium, lead, copper, zinc, and mercury in soil and soil solution in view of ecotoxicological effects. In Reviews of Environmental

Contamination and Toxicology, Springer, New York, pp 47-89.

Deleebeeck NME, De Schamphelaere KAC, Janssen CR. 2009. Effects of Mg2+ and H+ on

the toxicity of Ni2+ to the unicellular green alga Pseudokirchneriella subcapitata: Model development and validation with surface waters. Sci Total Environ 407: 1901-1914. Denmark. 2008, European Union risk assessment report. Nickel and nickel compounds.

Prepared by The Danish Environmental Protection Agency, on behalf of the European Union.

Di Toro DM, Allen HE, Bergman HL, Meyer JS, Paquin PR, Santore RC. 2001. Biotic ligand model of the acute toxicity of metals. 1. Technical basis. Environ Toxicol Chem 20: 2383-2396.

Dickson KL, Giesy JP, Wolfe L. 1994. Bioavailability: Physical, Chemical and Biological

Interactions. CRC, Boca Raton, FL, USA.

Dittbrenner N, Schmitt H, Capowiez Y, Triebskorn R. 2011. Sensitivity of Eisenia fetida in comparison to Aporrectodea caliginosa and Lumbricus terrestris after imidacloprid exposure. Body mass change and histopathology. J Soil Sediment 11: 1000-1010. Domínguez J. 2004. State of the art and new perspectives on vermicomposting research. In:

Edwards CA. (eds) Earthworm Ecology, 2nd ed. CRC Press LLC, Florida, USA, pp 401-424.

Doube BM, Schmidt O, Killham K, Correll R. 1997. Influence of mineral soil on the palatability of organic matter for Lumbricid earthworms: A simple food preference study.

Bibliography

130

Dudal Y, Gérard F. 2004. Accounting for natural organic matter in aqueous chemical equilibrium models: a review of the theories and applications. Earth-Sci Rev 66: 199- 216.

ECB. 2009. Europen union risk assessment report on nickel and nickel compounds. Ispra, Italy: European Chemicals Bureau.

ECI. 2008. Voluntary European Union risk assessment report. Copper, copper II sulphate pentahydrate, copper(I)oxide, copper(II)oxide, dicopperchloride trihydroxide. European Copper Institute.

Eisenhauer N, Marhan S, Scheu S. 2008. Assessment of anecic behavior in selected earthworm species: Effects on wheat seed burial, seedling establishment, wheat growth and litter incorporation. Appl Soil Ecol 38: 79-82.

Edwards CA, Bohlen PJ. 1996. Biology and Ecology of Earthworms. Chapman and Hall, London

Edwards CA, Arancon NQ. 2004. The use of earthworms in the breakdown of organic wastes

to produce vermicomposts and animal feed protein. In: Edwards CA. (ed) Earthworm

Ecology, 2nd edn. CRC Press LLC, Florida, pp 345-379.

Ehlers LJ, Luthy RG. 2003. Peer reviewed: contaminant bioavailability in soil and sediment.

Environ Sci Technol 37: 295A-302A.

Emmerling C, Strunk H. 2012. Active dispersal of the endo-anecic earthworm Aporrectodea

longa (Ude) in an experimental box. Soil Organisms 84: 491-498.

Erickson RJ. 2013. The biotic ligand model approach for addressing effects of exposure water chemistry on aquatic toxicity of metals: Genesis and challenges. Environ Toxicol

Chem 32: 1212-1214.

Fitzpatrick LC, Muratti-Ortiz JF, Venables BJ, Goven AJ. 1996. Comparative toxicity in earthworms Eisenia fetida and Lumbricus terrestris exposed to cadmium nitrate using artificial soil and filter paper protocols. Bull Environ Contam Toxicol 57:63-68.

Fraser PM, Boag B. 1998. The distribution of lumbricid earthworm communities in relation

to flatworms: a comparison between New Zealand and Europe. Pedobiologia 42:542-

553.

Gimeno-García, E.; Andreu, V.; Boluda, R. 1996. Heavy metals incidence in the application of inorganic fertilizers and pesticides to rice farming soils. Environ Pollut 92: 19-25. Gooddy DC, Shand P, Kinniburgh DG, Van Riemsdijk WH. 1995. Field based partition

coefficients for trace elements in soil solutions. Eur J Soil Sci 46: 265-285.

Groenenberg JE, Römkens PFAM, Comans RNJ, Luster J, Pampura T, Shotbolt L, Tipping E, De Vries W. 2010. Transfer functions for solid-solution partitioning of cadmium, copper, nickel, lead and zinc in soils: derivation of relationships for free metal ion activities and validation with independent data. Eur J Soil Sci 61: 58-73.

Haanstra L, Doelman P, Voshaar JHO. 1985. The use of sigmoidal dose response curves in soil ecotoxicological research. Plant Soil 84: 293-297.

Hamilton MA, Russo RC, Thurston RV. 1977. Trimmed Spearman-Karber method for estimating median lethal concentrations in toxicity bioassays. Environ Sci Technol 11: 714-719.

Hassler CS, Slaveykova VI, Wilkinson KJ. 2004. Some fundamental (and often overlooked) considerations underlying the free ion activity and biotic ligand model. Environ Toxicol

Chem 23: 283-291.

Hassler CS, Wilkinson KJ. 2003. Failure of the biotic ligand and free-ion activity models to explain zinc bioaccumulation by Chlorella kesslerii. Environ Toxicol Chem 22: 620-626. Hauschild MZ, Huijbregts MAJ, Jolliet O, MacLeod M, Margni M, Van de Meent D, Rosenbaum RK, McKone TE. 2008. Building a model based on scientific consensus for life cycle impact assessment of chemicals: the search for harmony and parsimony.

Environ Sci Technol 42: 7032-7037.

He E, Qiu H, Van Gestel CAM. 2014. Modelling uptake and toxicity of nickel in solution to

Enchytraeus crypticus with biotic ligand model theory. Environ Pollut 188: 17-26.

Heijerick DG, De Schamphelaere KAC, Janssen CR. 2002. Predicting acute zinc toxicity for

Daphnia magna as a function of key water chemistry characteristics: Development and

validation of a biotic ligand model. Environ Toxicol Chem 21: 1309-1315.

Hendrix PF, Bohlen PJ. 2002. Exotic Earthworm Invasions in North. America: Ecological and Policy Implications. Bioscience 52: 801-811.

Hobbelen PHF, Koolhaas JE, Van Gestel CAM. 2006. Bioaccumulation of heavy metals in the earthworms Lumbricus rubellus and Aporrectodea caliginosa in relation to total and available metal concentrations in field soils. Environ Pollut 144: 639-646.

Höfer T, Gerner I, Gundert-Remy U, Liebsch M, Schulte A, Spielmann H, Vogel R, Wettig K. 2004. Animal testing and alternative approaches for the human health risk assessment under the proposed new European chemicals regulation. Arch. Toxicol. 78: 549-64. Holmstrup M, Sørensen JG, Overgaard J, Bayley M, Bindesbøl AM, Slotsbo S, Fisker KV,

Maraldo K, Waagner D, Labouriau R, Asmund G. 2011. Body metal concentrations and glycogen reserves in earthworms (Dendrobaena octaedra) from contaminated and uncontaminated forest soil. Environ Pollut 159: 190-197.

Hopkin SP. 1989. Ecophysiology of Metals in Terrestrial Invertebrates. Elsevier Applied Science, London

Houba VJG, Lexmond TM, Novozamsky I, Van der LJJ. 1996. State of the art and future developments in soil analysis for bioavailability assessment. Sci Total Environ 178: 21- 28.

ISO. 2012. Soil quality -- Effects of Pollutants on Earthworms -- Part 1: Determination of acute toxicity to Eisenia fetida/Eisenia andrei ISO 11268-1: 2012; Part 2: Determination of Effects on Reproduction of Eisenia fetida/Eisenia andrei, ISO 11268-2: 2012. International Standardization Organization, Geneva.

Jager T. 2013. All individuals are not created equal; accounting for interindividual variation in fitting life-history responses to toxicants. Environ Sci Technol 47: 1664-1669. Jager T, Fleuren RHLJ, Hogendoorn EA, De Korte G. 2003. Elucidating the routes of

exposure for organic chemicals in the earthworm, Eisenia andrei (Oligochaeta). Environ

Sci Technol 37: 3399-3404.

Janssen CR, Heijerick DG, De Schamphelaere KAC, Allen HE. 2003. Environmental risk assessment of metals: tools for incorporating bioavailability. Environ Int 28: 793-800. Janssen MPM, Bruins A, De Vries TH, Van Straalen NM. 1991. Comparison of cadmium

Bibliography

132

Janssen RPT, Posthuma L, Baerselman R, Den Holander HA, Van Veen RPM, Peijnenburg WJGM. 1997. Equilibrium partitioning of heavy metals in Dutch soils. II. Prediction of

metal accumulation in earthworms. Environ Toxicol Chem 16: 2479-2488.

Jho EH, An J, Nam K. 2011. Extended biotic ligand model for prediction of mixture toxicity of Cd and Pb using single metal toxicity data. Environ Toxicol Chem 30: 1697-1703. Jihen EH, Fatima H, Nouha A, Baati T, Imed M, Abdelhamid K. 2010. Cadmium retention

increase: A probable key mechanism of the protective effect of zinc on cadmium- induced toxicity in the kidney. Toxicol Lett 196: 104-109.

Jihen EH, Messaoudi I, Hammouda F, Kerkeni A. 2009. Protective effects of selenium (Se) and zinc (Zn) on cadmium (Cd) toxicity in the liver of the rat: effects on the oxidative stress. Ecotoxicol Environ Saf 72: 1559-1564.

Jihen EH, Messaoudi I, Fatima H, Kerkeni A. 2008. Protective effects of selenium (Se) and zinc (Zn) on cadmium (Cd) toxicity in the liver and kidney of the rat: histology and Cd accumulation. Food Chem Toxicol 46: 3522-3527.

Jonker MJ, Svendsen C, Bedaux JJM, Bongers M, Kammenga JE. 2005. Significance testing of synergistic/antagonistic, dose level-dependent, or dose ratio-dependent effects in mixture dose-response analysis. Environ Toxicol Chem 24: 2701-2713.

Jonker MJ, Sweijen RAJC, Kammenga JE. 2004. Toxicity of simple mixtures to the nematode Caenorhabditis elegans in relation to soil sorption. Environ Toxicol Chem 23: 480-488.